(+/-)-4-(2-tert-butyldimethylsilyloxy)ethyl-3-(p-toluenesulfonyl)-Δ^3,4-quinolizidine

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹嗪类
• 英文名称: (+/-)-4-(2-tert-butyldimethylsilyloxy)ethyl-3-(p-toluenesulfonyl)-Δ^3,4-quinolizidine
• 英文别名: tert-butyl-dimethyl-[2-[3-(4-methylphenyl)sulfonyl-2,6,7,8,9,9a-hexahydro-1H-quinolizin-4-yl]ethoxy]silane
• 化学式: C₂₄H₃₉NO₃SSi
• 分子量: 449.73
• InChiKey: AGRHJEOTXWWTKV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.04
• 重原子数：
  30
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  55
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  2-哌啶乙醇 在 氯化亚砜 作用下， 以 四氢呋喃 为溶剂， 生成 (+/-)-4-(2-tert-butyldimethylsilyloxy)ethyl-3-(p-toluenesulfonyl)-Δ^3,4-quinolizidine
  参考文献：
  名称：

  Synthesis of Substituted Piperidines, Indolizidines, Quinolizidines, and Pyrrolizidines via a Cycloaddition Strategy Using Acetylenic Sulfones as Alkene Dipole Equivalents

  摘要：

  The conjugate additions of beta- and gamma-chloroamines to acetylenic sulfones afford enamine sulfones, which then undergo intramolecular alkylation to produce the corresponding cyclic enamines, This provides a convenient route to substituted piperidines, indolizidines, quinolizidines, and pyrrolizidines. The enantioselective total synthesis of the alkaloid (-)-indolizidine 167B (also named gephyrotoxin 167B) was thus achieved by the cycloaddition of (S)-2-(2-chloroethyl)pyrrolidine to 1-(p-toluenesulfonyl)-1-pentyne, followed by stereoselective reduction of the enamine moiety and reductive desulfonylation.

  DOI：

  10.1021/ol990592u

文献信息

• A Convenient New Route to Piperidines, Pyrrolizidines, Indolizidines, and Quinolizidines by Cyclization of Acetylenic Sulfones with β- and γ-Chloroamines. Enantioselective Total Synthesis of Indolizidines <b>(</b><b>−</b><b>)-167B</b>, <b>(</b><b>−</b><b>)-209D</b>, <b>(</b><b>−</b><b>)-209B</b>, and <b>(</b><b>−</b><b>)-207A</b>
  作者：Thomas G. Back、Katsumasa Nakajima

  DOI：10.1021/jo000080p

  日期：2000.7.1

  the corresponding 2- or 2,6-disubstituted piperidines, while 2-(chloromethyl)pyrrolidines, 2-(2-chloroethyl)pyrrolidines, 2-(chloromethyl)piperidines, and 2-(2-chloroethyl)piperidines produced the corresponding 3-substituted pyrrolizidines, 5- or 3-substituted indolizidines, and 4-substituted quinolizidines, respectively. 8-Methyl-5-substituted indolizidines were also prepared from the appropriate methyl-substituted

  （L）-苯丙氨酸和（L）-蛋氨酸的甲酯通过其游离氨基与1-（对甲苯磺酰基）己炔进行共轭加成反应，随后将相应的酰胺阴离子进行分子内酰化和互变异构化，得到2-苄基- 5-正丁基-3-羟基-4-（对甲苯磺酰基）吡咯和5-正丁基-3-羟基-2-（2-甲硫基乙基）-4-（对甲苯磺酰基）吡咯。一系列无环和环状仲β-和γ-氯胺在炔属砜上的共轭加成在温和的条件下类似地进行。将所得的加合物在-78℃下用LDA在THF中的去质子化，并将所得的砜稳定的碳负离子进行分子内烷基化，得到环状烯胺砜。因此，无环的γ-氯烷基-苄胺提供了相应的2-或2，6-二取代的哌啶，而2-（氯甲基）吡咯烷，2-（2-氯乙基）吡咯烷，2-（氯甲基）哌啶和2-（2-氯乙基）哌啶产生相应的3-取代的吡咯烷，5-或3 -取代的吲哚嗪和4-取代的喹oli啶。还由适当的甲基取代的氯胺前体制备8-甲基-5-取代的吲哚并核苷。对映选择性合成是通过使用
• Synthesis of Substituted Piperidines, Indolizidines, Quinolizidines, and Pyrrolizidines via a Cycloaddition Strategy Using Acetylenic Sulfones as Alkene Dipole Equivalents
  作者：Thomas G. Back、Katsumasa Nakajima

  DOI：10.1021/ol990592u

  日期：1999.7.1

  The conjugate additions of beta- and gamma-chloroamines to acetylenic sulfones afford enamine sulfones, which then undergo intramolecular alkylation to produce the corresponding cyclic enamines, This provides a convenient route to substituted piperidines, indolizidines, quinolizidines, and pyrrolizidines. The enantioselective total synthesis of the alkaloid (-)-indolizidine 167B (also named gephyrotoxin 167B) was thus achieved by the cycloaddition of (S)-2-(2-chloroethyl)pyrrolidine to 1-(p-toluenesulfonyl)-1-pentyne, followed by stereoselective reduction of the enamine moiety and reductive desulfonylation.